Using aluminum isopropoxide as the raw material and dilute nitric acid as the solving agent, the spherical γ-Al2O3 with porous structure was successfully prepared by the sol-oil-ammonia drop method. The effects of alcohols with different carbon chain lengths as pore-expanding agents on their porous structure were investigated. The structure was characterized by XRD, FT-IR, SEM, TG, DTG and specific surface area and pore size analyzers. The results show that the type of organic alcohol has an effect on the porous structure of spherical γ-Al2O3. The longer the carbon chain alcohol, the richer the pore structure of the spherical γ-Al2O3 prepared; Larger, can reach 270.9 m2 / g. The spherical γ-Al2O3 with high sphericity and rich pore structure can be further used in catalysis, adsorption and other fields.